The earliest work relating to the manufacture of amines by the amination of olefins, particularly ethylamines by the amination of ethylene, appears to have been done by Teter, et al. as noted in U.S. Pat. Nos. 2,623,061; 2,479,879; 2,471,892; 2,381,470; 2,658,041; 2,381,709; 2,392,107 and 2,398,899. These patents show that ammonia can be made to react with olefins, e.g. ethylene to produce amine. As noted by others through improvements in the process, substantial quantities of polyamines and polyolefins were produced by the Teter, et al. catalyst which is a metal supported on a spinel-type support, silica and diatomaceous earth and the like.
Olin, et al. in U.S. Pat. Nos. 2,422,631 and 2,422,632, discloses a process for producing amines and amides by the reaction of a mono-unsaturated olefin, carbon monoxide and an amine or ammonia. The catalyst used is a combination of a dehydrating and a hydrogenation catalyst, e.g. nickel and activated alumina, copper and silica gel, etc.
Whitman, U.S. Pat. No. 2,501,556 discloses a liquid phase reaction of ammonia and ethylene in the presence of an alkali metal catalyst to form ethylamine.
Ritter, et al. in an article entitled "A New Reaction of Nitriles.I.Amides From Alkenes and Mononitriles" disclosed the reaction whereby an olefin is reacted with hydrogen cyanide in the presence of sulfuric acid to form an amide. The amide is subsequently hydrolyzed to form the corresponding amine. See J Am. Chem. Soc. 70, 4045 (1948).
McClain, U.S. Pat. No. 3,412,158, discloses a gas phase process for producing primary alkylamines from low molecular weight olefins and ammonia by carrying out the gas phase process in the presence of a noble metal containing catalyst at temperature of from 90.degree. to 175.degree. C., and at pressures of from atmospheric to 2,000 psig.
Peterson et al. in U.S. Pat. Nos. 4,307,250 and 4,375,002 disclose the catalytic amination of a C.sub.2 -C.sub.8 olefin using a synthetic crystaline alumino silicate or a naturally occuring zeolite as a catalyst. Various olefins, such as ethylene, propylene, and isobutylene are reacted with ammonia or an amine in the presence of the zeolite catalyst to produce the amine product.